Chemistry Year 12 - NZ Science Class Online

Chemistry Year 12 - NZ Science Class Online

Chemistry AS 91392 C3.6 Aqueous Systems Achievement Criteria - Solubility Demonstrate understanding of equilibrium principles in aqueous systems Aqueous systems are limited to those involving sparingly soluble ionic solids Equilibrium principles in aqueous systems are limited to qualitative descriptions and/or calculations involving: relative concentrations of dissolved species sparingly soluble ionic solids relating solubility to Ks AS 91392 C3.6 solubility of solids in water and in solutions already containing one of the ions A or B (a common ion) or due to the formation of a complex ion, or the reaction of a basic anion with added acid predicting precipitation or dissolution Sparingly soluble ionic solids are limited to AB, A 2B and AB2 types where neither of the ions A nor B reacts further with water. Achievement Criteria Acids and Bases Demonstrate understanding of equilibrium principles in

aqueous systems Aqueous systems are limited to those involving acidic and basic solutions (in which proton transfer occurs). acidic and basic solutions (includes buffers) acid/base strength, Ka (pKa) AS 91392 C3.6 concentration of species present in weak acidic and/or basic solutions (includes buffers) relating concentration of species to pH and conductivity titration curves to represent an acid-base system including selection of indicators (titrations of weak acids with weak bases are excluded). Acidic and basic solutions are monoprotic acids, bases, salts, and buffers (those in which the extent of reaction is small so that the equilibrium concentration of a dissolved weak acid or base can be approximated by the initial concentration). Equilibrium Some reactions go to completion reactants products Reaction stops when one of the reactants is used up

Other reactions are reversible products reactants Products are also forming reactants. Reaction continues Equilibrium is a state of dynamic balance where the rates of formation of product = equals the rate of formation of reactants At equilibrium the concentrations of reactants and products are constant. However, both the forward and reverse reactions are continuing Ba Kn ck ow gro le un dg d e Equilibrium When a reaction has reached equilibrium then the proportion of reactants is fixed in relation to the proportion of products. Reactants particles are still colliding to form products but the same number of products are colliding (or breaking apart) to form reactants. The proportion of reactants to products depends upon the reaction and the environmental conditions of a reaction such as temperature, pressure and concentration.

On the left hand side the proportion of products will be higher than the reactants and on the right hand side the proportion of reactants will be higher than products. Ba Kn ck ow gro le un dg d e Equilibrium Evapouration case study A dynamic equilibrium must occur in a closed system where all reactants and products are retained in an area where particles can collide with each other. The example below shows a system where liquid water is evapourating into a gas. In an open system the gas will escape and gradually the water level will decrease. In a closed system, where the lid prevents the gas escaping, the proportion of liquid to gas will become fixed at a dynamic equilibrium. Liquid will evapourate into gas at the same rate that gas condenses into a liquid. Equilibrium Constant: KC The size of K calculated gives information as to how far a reaction has proceeded

Large K value eg K=10000 Small K value eg K=0.0001 Large amount of products produced. Small amount of products produced . Reaction is close to completion when Reaction only just underway when equilibrium was reached r products equilibrium was reached reactants Note: equilibrium does not mean there are equal amounts of reactants and products present p

Ba Kn ck ow gro le un dg d e Changes in Equilibrium A system stays in equilibrium unless a change is made A change made to a system in equilibrium will either Eventually equilibrium is re-established and the rate of forward reaction again equals rate of reverse reaction Solubility The solubility of a substance is the amount of that substance that will dissolve in a given amount of solvent. Solubility is a quantitative term. Solubility's vary depending on the solvent and the solute. The terms soluble and insoluble are relative. Some substances can be sparingly soluble where only a very small percentage dissolves. For a solute to dissolve the attraction to the solvent molecules must be stronger than the bonds holding the atoms/molecules of the solute together. Ba Kn ck

ow gro le un dg d e Solution (saltwater) Aqueous Solutions A solution is made up of a solvent and a solute. A solvent is a substance such as water that is able to dissolve a solute. A solution where the solvent is water is called aqueous. The solvent pulls apart the bonds that hold the solute together and the solute particles diffuse Solute (spread randomly by hitting into each other) throughout the (salt) solvent to create a solution. The Solvent solution is a mixture with evenly (water) spread solvent and solute particles. These particles can be physically separated by evaporation.

Ba Kn ck ow gro le un dg d e Aqueous Solutions When a solid mixes into a liquid and can longer be seen it has dissolved. The liquid is called the solvent and it pulls apart the bonds between the solid particles, called the solute, and they diffuse. A solution is then created when the solvent particles (often water) are mixed up with the broken apart solute particles. For a solute to dissolve, the solvent particles must form bonds with the solute particles that are of similar strength, to the bonds between the solute particles. Water, being polar

attracts ions because they are charged and so Ba Kn ck ow gro le un dg d e The structure of Ionic Solids Metal + NonMetal An ionic solid is made up of ions held together by strong directional electrostatic forces (ionic bonding) between +ve (cations) and ve (anions) ions in a 3-dimensional lattice. Equilibrium of solutions A system reaches equilibrium when the rate the solid dissociates into ions matches the rate that the ions precipitate into solids. The equilibrium can be changed by adjusting the system temperature, pressure or adding/removing reactants/product.

Sparingly Solubility Many ionic salts are sparingly soluble in water. Even those that are commonly classified as insoluble still have a small amount of the solid dissolved in an aqueous solution so that when the solution is saturated an equilibrium exists between the dissolved ions and the insoluble solid. The solubility of a salt is often measured in grams per litre, g L-1, or moles per litre, mol L-1. This is the number of grams or moles of the solid that will dissolve to make up 1 litre of a saturated solution at that temperature. If the solubility of a pure salt is given then it is possible to calculate the concentration of both the cation and anion in the solution. Sparingly Soluble Equilibrium Equations When sparingly soluble ionic salts dissolve in water to form aqueous solutions a small percentage of the salt dissociates into individual ions (anion and cation) in the same ratio that they exist as a solid salt. Once the aqueous solution reaches equilibrium, the rate that the solid salt dissociates into the ions (breaking bonds holding solid together) is matched by the rate the ions reform ionic bonds and reassemble as an ionic solid in the solution.

NOTE: although we use an equation, dissolving is a physical change rather than a chemical reaction. Ag2CrO4(s) 2Ag+(aq) + CrO42(aq) Water is not included in the equation because the very large concentration before and after means Solubility [s] and Concentration At room temperature the solubility of silver chromate, Ag 2CrO4,is 6.5 x 10-5 mol L-1. What is the concentration of Ag+ and CrO42- ions [s] in 500 mL of a saturated solution? Start with the equation for the dissolving process. Ag2CrO4(s) 2Ag+(aq) + CrO42(aq)

The equation shows that for every mole of dissolved solid there are 2 moles of Ag+ ions and 1 mole of CrO42 ions. Therefore [Ag+] = 2 x 6.5 x 10-5 = 1.3 x 10--9 mol L-1 [CrO42] = 6.5 x 10-5 mol L-1 Note: that because the calculation involves concentration it does not matter that the sample is a 500 mL sample rather than a litre sample since the concentration in any volume [ ] indicate s concent ration Solubility from molL-1 to gL-1 Example question: What is the solubility [s] of Ag2CrO4 in g L-1? To convert from moles per litre to grams per litre it is necessary to use the molar mass M(Ag2CrO4) = 332 g mol-1 and the relationship s= 6.5 x 10-5 mol L-1. Since there is 6.5 x 10-5 moles in 1 litre the number of grams in 1 litre would be mass = 6.5 x 10-5 x 332

= 0.0216 grams and the concentration is 0.0216 g L-1. m = n x M. Equilibrium Constant: Kc A equilibrium equation can be written as an expression (Kc) in which concentrations of products and reactants can be placed in to give us a value. The value will indication the proportion of reactants to products in any given reaction. Given aA + bB e.g. N2(g) + 3H2 (g) Kc = [ C ] c x [D]d [ A ]a x [B]b e.g. Kc = [ NH3 ] 2 [ N2 ] x [ H2 ] 3

[ Note: only reactants and cC + dD products in gas state or aqueous 2NH3 (g) can be placed into an equilibrium ] = concentrationexpression. in molL-1 Do at equilibrium not place solids or liquids into the expression. Products are divided by reactants and the number of mols in the equation is written to the power of each reactant and product. Solubility product Ks The solubility product is the equilibrium constant for the equilibrium between an undissolved salt and its ions in a saturated solution. It is very similar to any

other equilibrium constant and, for any particular salt, the value of Ks only changes if temperature changes. Remember: Water is not included in Consider a saturated solution of Ca(OH)2. For this the equation or equilibrium we have the solubility product expression expression because the very Ca(OH)2(s) Ca2+(aq) + 2OH(aq) large concentration Ks (Ca(OH)2) = [Ca2+] [OH]2 before and after means there is negligible change water OH-(aq) Ca(OH)2(s) Ca2+(aq) Solubility product Ks Exercise For each of the following sparingly soluble salts write the equation for the solid dissolving, calculate the concentration of each ion [s] and then the expression for the solubility product [Ks].

(a) CaCO3(s) 1.3 x 10-4gL-1 (b) Ag2S(s) 2.8 x 10-3 gL-1 (c) PbI2(s) (d) Fe(OH)3(s) 6.4 x 10-2gL-1 A 4.2 x 10-5 gL-1 cC + dD Ks = [ C ] c x [ D ] d [ ] = concentration in molL-1at equilibrium Remember: The solid salt is not included in the expression only the ions in aqueous state.

NOTE: If there is a 2:1 or 1:2 ratio of ions in the salt, the appropriate ion concentration must be multiplied AND also squared in the Ks expression. 2015 Solubility equations - NCEA Case Study Achieved Question Question: 2a: (i) Sufficient calcium carbonate, CaCO3(s), is dissolved in water to make a saturated solution. Write the equation for the equilibrium occurring in a saturated solution of CaCO3. CaCO3(s) Ca2+(aq) + CO32(aq) Question: 2a: (ii) Write the expression for Ks(CaCO3). Ks = [Ca2+][CO32] 2014 solubility equations - NCEA Case Study Achieved Question Question: 2a: A flask contains a saturated solution of PbCl2 in the presence of undissolved PbCl2. (i) Write the equation for the dissolving equilibrium in

a saturated solution of PbCl2. PbCl2(s) Pb2+(aq) + 2Cl(aq) Question: 2a: (ii) Write the expression for Ks(PbCl2). Ks = [Pb2+][Cl]2 Calculating Ks : ratio of cation to anion 1:1 Since the solubility can be used to calculate the concentration of ions in a saturated solution of a sparingly soluble salt, then these concentrations can be used to calculate the value of Ks. 1. AB type of salt (ratio of cation to anion = 1:1) The solubility of BaSO4 is given as 1.05 x 10-5 mol L-1 at 25oC. Calculate the value of Ks. BaSO4(s) From this equation Ba2+ (aq) + SO42 (aq) [Ba2+] = [SO42-] = solubility, s

Ks = s2 Ks (BaSO4) = [Ba2+] x [SO42] = s2 = (1.05 x 10-5)2 = 1.10 x 10-10 NOTE: This equality is only true if there are no other sources of Ba2+ and SO42 present in the solution ie if all the Ba2+ and SO42 ions come from 2015 Solubility equations - NCEA Case Study Question: 2a: (iii) Calculate the solubility product of CaCO 3, Ks(CaCO3). The solubility of CaCO3 is 5.74 105 mol L1. Ks(CaCO3) = (5.74 105)2 = 3.29 109 Merit Question Determining Ks : ratio of cation to anion 2:1 or 1:2 AB2 (or A2B) type of salt (ratio cation to anion = 1:2 OR 2:1) Calculate the solubility product for PbI2 at 25 oC, given the solubility at 25 oC is 1.52 x 10-3 mol L-1. PbI2(s) This tells us that

Pb2+(aq) + 2I (aq) [Pb2+] = solubility, s = 1.52 x 10-3 mol L-1 and [I] = 2 x solubility = 2s = 2 x 1.52 x 10-3 = 3.04 x 10-3 mol L-1 The expression for Ks is Ks (PbI2) = [Pb2+] x [I-]2 and substituting for solubility we get Ks (PbI2) = (1.52 x 10-3) x (3.04 x 10-3)2 = 1.40 x 10-8 Ks = 4s3 NOTE: because [2s]2 means everything inside the brackets is squared then expanding it out becomes 22 + s2 = 4s2. The other ion [s] then is multiplied so Determining S from Ks (1:1) It is possible to use the value of Ks at any particular temperature to calculate the solubility of the salt [s] at that temperature and also to calculate the concentration of ions in the saturated solution. Example 1.

Calculate the solubility of iron(II) sulfide at 25 oC given that FeS(s) Fe2+(aq) + S2(aq) Ks (FeS) = [Fe2+] x [S2] = 6.3 x 10-18 From the equation it can be seen that, since the only source of ions is from the dissolving of FeS then [Fe2+] = [S2] = solubility, s Ks (FeS) = s2 and s = = = 2.51 x 10-9 mol L-1 s = Ks Determining S from Ks (2:1) 3 s = Ks Calculate the solubility of zinc hydroxide at 25 oC given Ks (Zn(OH)2) 4

= 2.0 x 10-17 The dissolving equation is Zn(OH)2(s) Zn2+(aq) + 2OH (aq) This means that [Zn2+] = solubility = s and [OH] = 2 x solubility = 2s The expression for Ks is Ks (Zn(OH)2) = [Zn2+] x [OH]2 OR Ks (Zn(OH)2) = (s) x (2s)2 = 4s3 It is therefore possible to use this expression to solve for the solubility, s. 3 s= Ks 4 = = 1.71 x 10-6 mol L-1 From the solubility it is possible to then calculate the concentration of the ions. [Zn2+] = solubility = 1.71 x 10-6 mol L-1

Merit Question 2014 calculating s - NCEA Case Study Question: 2a: (iii) Calculate the solubility (in mol L1) of lead(II) chloride in water at 25C, and give the [Pb2+] and [Cl] in the solution. Ks(PbCl2) = 1.70 105 at 25C [Pb2+] = x Ks = 4x3 x= 3 [Cl] = 2x Ks 4 5 1.70 10 =3 4 =1.62 10 2 mol L 1 [Pb2+] = 1.62 102 mol L1

[Cl] = 3.24 10 mol L1 3 s = Ks 4 Effects of Acid on Solubility If the salt contains a carbonate i.e. Ag2CO3 which is sparingly soluble, it will dissociate into its ions one ion being a cation and the other the anion carbonate. Ag2CO3 Ag+ + CO32- Acid neutralises carbonates If acid is added to this system then it will react with the carbonate ion effectively reducing the concentration of this in the solution. Accordingly to the principals of equilibrium if a product is removed (carbonate) the reaction will increase in the forward direction to replace the depleted product hence more salt will dissolve and the overall solubility of the system will increase. Acids increase solubility if the salt contains a carbonate Effects of Base on Solubility

If a sparingly soluble salt contains an cation i.e. AgCl containing Ag + which reacts with NH3 or OH- to produce a complex ion such as [Ag(NH3)2]+ Base locks up many cations into complex ions Then when a base is added to this system then it will react with the cation effectively reducing the concentration of this in the solution. Accordingly to the principals of equilibrium if a product is removed (silver ions) the reaction will increase in the forward direction to replace the depleted product hence more salt will dissolve and the overall solubility of the system will increase. Bases increase solubility if the salt contains a cation that forms a complex ion When pH is above 10 Effects of adding hydroxide on Solubility Decrease SOLUBILITY If a sparingly soluble salt contains hydroxide i.e. Zn(OH) 2 , a small amount of OHadded will decrease solubility as the reaction is shifted to the left to remove added product and produce more reactant (the solid salt) Bases decrease solubility if the salt contains a hydroxide ion This occurs when pH is above 4 but below 10

Increase SOLUBILITY Then when excess hydroxide is added to this system then it will react with the cation to produce a complex ion, effectively reducing the concentration of this in the solution. Accordingly to the principals of equilibrium if a product is removed (silver ions) the reaction will increase in the forward direction to replace the depleted product hence more salt will dissolve and the overall solubility of the system will increase. Bases increase solubility if the salt contains a cation that forms a complex ion When pH is above 2015 Solubility and Acid - NCEA Case Study Merit Question Question: 2b: Some marine animals use calcium carbonate to form their shells. Increased acidification of the oceans poses a problem for the survival of these marine animals. Explain why the solubility of CaCO3 is higher in an acidic solution. Use an equation to support your explanation. The H3O+ from the acidic solution reacts with the CO32. This reduces [CO32], causing the

equilibrium to shift towards the products / RHS to replace some of the lost CO32. Therefore more solid CaCO3 will dissolve. 2H3O+ + CO32 3H2O + CO2 2014 solubility and acid - NCEA Case Study Excellence Question Question: 2c: The solubility of zinc hydroxide, Zn(OH)2, can be altered by changes in pH. Some changes in pH may lead to the formation of complex ions, such as the zincate ion, [Zn(OH)4]2 Use equilibrium principles to explain why the solubility of zinc hydroxide increases when the pH is less than 4 or greater than 10. Zn(OH)2(s) Zn2+(aq) + 2OH(aq) When pH is less than 4 / low, [OH] is decreased due to the reaction with H3O+ to form water, H3O+ + OH H2O so equilibrium shifts to the right to produce more [OH ], therefore more Zn(OH)2 will dissolve. When pH is greater than 10 / high, then more OH is available and the complex ion (zincate ion) will form. Zn(OH)2(s)+ 2OH [Zn(OH)4]2 OR Zn2+ + 4OH [Zn(OH)4]2 This decrease in [Zn2+] causes the position of equilibrium to shift further to the right, therefore more Zn(OH)2 dissolves. The ratio of the

Ionic product concentrations of products reactants called Q. In any solution, whether it is saturated orand not, such as AgCl theis product formed [Ag+][Cl-] is called the ionic product and can not exceed the Ks. If either Ag+ ions or Cl- ions are added from another source, such as by adding NaCl, and the new concentrations of ions exceed the Ks then a precipitate will form. Example What is the minimum concentration of Cl- ions to give a precipitate of AgCl? c(AgNO3) = 0.01molL-1 Ks = 2 x10-10 If IP > Ks then precipitate will form 1. AgCl(s) Ag+(aq) 2. Ks = [Ag+] [Cl-] +

Cl-(aq) Ks = [0.01] [Cl-] 3. Rearrange Ks = [Ag+] [Cl-] [Cl-] = Ks [0.01] = 2 x 10-10 Ks is the maximum concentration of ions the solution can hold (at a given temperature) = 2 x 10-8 0.01 A precipitate will form if the concentration of Cl- ions exceeds 2 x 10-8 molL-1 Common ion effect

Ks is used to calculate the solubility of sparingly soluble salts in pure water. If a solution being added contains either one of the ions already present in the solution then this will reduce the solubility of the salt since the presence of the common ion will move the equilibrium towards the side of precipitated salt. For example, the equation for the dissolving of AgCl is AgCl(s) Ag+(aq) + Cl(aq) AgCl would be less soluble in sea water than in pure water because the presence of the Cl dissolved in the sea water means [Cl] is higher which must reduce the concentration of [Ag+] at equilibrium (as the value of Ks cannot change). This reduces the amount of solid AgCl that can dissolve. Common ion effect Common Ion effect an example of Le Chateliers principle. It is possible to calculate the solubility of any salt in a solution containing a common ion, provided the concentration of the ion in the solution and the Ks is known. Example What is the solubility of AgCl in a 0.0025 mol L-1 solution of NaCl?

Ks (AgCl) = [Ag+] x [Cl-] = 1.6 x 10-10 [Ag+] = solubility, s of the AgCl since the only source of silver ions is from dissolved AgCl. [Cl-] = 0.0025 + s since the final concentration of Cl- ions is given by the concentration originally in the solution PLUS the extra dissolved NOTE:(a) This to make a saturated solution. solubility of AgCl in a Assume s is much less than 0.0025 and therefore [Cl-] = 0.0025 solution containing Cl ion is much less than Ks (AgCl) = s x 0.0025 = 1.6 x 10-10 (in this case by more and s = 1.6 x 10 -10 than 1000x) the 0.0025 solubility in pure water of 1.26 x 10-5 = 6.4 x 10-8 mol L-1. mol L-1. 2015 Common Ion effect - NCEA Case Study Excellence Question Question: 2c: Show, by calculation, that a precipitate of lead(II) hydroxide,

Pb(OH)2, will form when 25.0 mL of a sodium hydroxide solution, NaOH, at pH 12.6 is added to 25.0 mL of a 0.00421 mol L 1 lead(II) nitrate, Pb(NO3)2, solution. Ks(Pb(OH)2) = 8.00 1017 at 25C The ratio of the concentrations of products and reactants is called Q. Pb(OH)2 Pb2+ + 2OH Q = [Pb2+][OH] 2 [Pb2+] = 0.5 0.00421 = 2.105 103 [OH] = 0.5 0.0398 = 1.99 102 Q = (2.105 103) (1.99 102)2 Q = 8.34 107 Since Q > Ks, a precipitate of Pb(OH)2 will form. pH =12.6 pOH = 1.4 [OH] = 0.0398 2014 common ion effect - NCEA Case Study Excellence Question

Question: 2b: A sample of seawater has a chloride ion concentration of 0.440 mol L1. Determine whether a precipitate of lead(II) chloride will form when a 2.00 g sample of lead(II) nitrate is added to 500 mL of the seawater. Ks(PbCl2) = 1.70 105 M(Pb(NO3)2) = 331 g mol1 n(Pb(NO3)2) = 2.00 g 331 g mol 1 = 6.04 103 mol [Pb2+] = 6.04 103 mol / 0.500L = 1.21 102 mol L1 Q = (1.21 102) x (0.440)2 = 2.34 103 As Q > Ks, a precipitate will form. Solubility Key concepts equatio ns + C

C2A + + 2C CA2 + A- C+ 2A- CA + A- Equilibrium effects Solubility expressions Ks(CA) = [C] [A] =

Ks(C2A) 2 [C] [A] Ks(CA = 2) [C] [A]2 Ks/s calculations Ks(CA) s(CA) = s22A) Ks(C = 4s3C = = 3 k s s(C2A) = kA/4

cation s = anion Common ion effect If IP > Ks then precipitate If IP < Ks then no precipitate IP = ionic product Ks = solubility Ba Kn ck ow gro le un dg d e Acids their characteristics Acids are a family of substances which all show acidic

characteristics or properties. These properties relate to how the acids react with other chemicals. They have a sour taste and react with metals. Acids can be found in nature and called organic acids or manufactured in the laboratory and called mineral acids. Acids their characteristics An Acid donates its Hydrogen ion (H+) , which is really just a proton - the electron remains behind. Common acids include the strong acids HNO3 - nitric acid, HCl hydrochloric acid, H2SO4 sulfuric acid, and the weak acid CH3COOH ethanoic acid. Ba Kn ck ow gro le un dg d e Bases have a slippery

feel to them and common house hold bases include floor clearers and antacid tables to fix indigestion. Bases that dissolve into water are called an alkali, and produce OHions. Bases their characteristics Bases are a family of Chemicals that can remove acid particles (H+) from a solution. They have opposite properties from acids. Bases their characteristics A Base accepts a Hydrogen ion that have been donated from an Acid. Common bases include the strong bases NaOH sodium hydroxide, KOH potassium hydroxide and the weak base NH3 ammonia. NH3 + H2O NH4+ Some

substances such as water are amphiprotic and can act as both an acid or a base depending on what other substance the water is with. + OH- BrnstedLowry theory of Acid and Base reactions Acid-Base reactions involve the transfer of Hydrogen ions, H+ A hydrogen ion, H+ is simply a lone proton (an H with the electron removed) In water (or aqueous solutions ) H+ ions exist as an H3O+ ion, called hydronium. Acids are substances that donate protons (H+) in solution Bases are substances that accept protons (H+) in solution HCl(g) + H2O(l)

NH3(g) + H2O(l) H3O+(aq) + Cl-(aq) NH4+(aq) + OH-(aq) HCl gas dissolved in water NH3 gas dissolved in water HCl has donated a H+ so is acting as an acid NH3 has accepted a H+ so it is acting as a base H2O has accepted a H+ so it is acting as a base H2O has donated a H+ so is acting as an acid Solution becomes acidic since H3O+ ions form

Solution becomes basic since OH- ions form. Amphiprotic substances An amphiprotic substance is a substance that can donate or accept a proton, H+ For a substance to be amphiprotic it must 1.contain a hydrogen atom which is able to be donated to another chemical species. 2.be able to accept a hydrogen ion from another species. Examples of amphiprotic species include, H2O, HCO3- , HSO4- , HPO42- and H2PO4Name Chemical of amphiproti Able to donate a proton, H+ Able to accept a proton, H+ formula c species H2O H2O(l) H+(aq) + OH-(aq) H2O(l) + H+(aq) H3O+(aq) Water HCO3-(aq) + H+(aq) Hydrogen HCO3HCO3-(aq) H+(aq) + CO32-(aq) carbonate ion H2CO3(aq) Hydrogen sulfat HSO4HSO4-(aq) H+(aq) + SO42-(aq) HSO4-(aq) + H+(aq) H2SO4(aq)

e ion Dihydrogen phosphate ion H2PO 4 H2PO4-(aq) H+(aq) + HPO42(aq) H2PO4-(aq) + H+(aq) H3PO4(aq) Ba Kn ck ow gro le un dg d e strong and weak acids and bases You can define acids and bases as being "strong" or "weak". Strong acids are compounds that completely dissociate

(break up) in water. All of the H+ ions (protons) break away from the original acid molecule in water. A weak acid only partially dissociates and loses just some of its H+ ions (protons) in water. For strong bases, all of the OH- ions break away from the molecule in water. Ba Kn ck ow gro le un dg d e strong and weak bases You can define bases as being "strong" or "weak". Strong bases are compounds where each molecule will

accept an H+ ion. A weak base is a compound where only some of the molecules will accept a H+ ion. Most weak base molecules remain un reacted. Note: For strong alkalis, all of the OHions break away from the molecule in water. Strong and Weak Acids The strength of an acid is determined by how readily it will donate its H + ions. Strong acids will have a low pH (0-3) and include HCl, H 2SO4 and HNO3. Weak acids will have a higher pH (4-6). They are mostly organic acids and include CH3COOH. Weak acids Strong acids Donate protons (H+) in aqueous solution to become completely dissociated. HCl(g) + H2O(l) H3O+(aq) + Cl-(aq) HCl gas dissolved in water

HCl has donated a H so is acting as an acid + H2O has accepted a H+ so it is acting as a base Solution contains virtually no intact HCl molecules after reaction. Donate protons (H+) in aqueous solution to become partially dissociated. CH3COOH(l) + H2O(l) CH3COO-(aq) + H3O+(aq) CH3COOH dissolved in water Only some of the acetic acid molecules dissociate into acetate ions (CH3COO-) Because the acetate ion is a strong base (conjugate pairs) it will readily accept H+ (from H3O+) and become acetic acid. Solution contains mostly intact CH3COOH molecules. Strong and Weak Bases The strength of an base is determined by how readily it will accept H + ions. Strong bases will have a high pH (12-14) and include NaOH and KOH. Weak acids

will have a lower pH (8-11). They include NH3. Strong Bases Weak Bases Completely accept protons (H+) in aqueous solution Partially accept protons (H+) in aqueous solution NaOH(s) NH3(g) + H2O H 2O Na+(aq) + OH-(aq) NH4+(aq) + OH-(aq) NaOH completely dissociates The OH- ions will readily accept H+ ions. Solution contains very few intact NaOH molecules after reaction.

Only some of the ammonia molecules dissociate into ammonium ions (NH4+) Because ammonium is a reasonably strong acid (conjugate pairs) it will readily donate H+ and become ammonia. Solution contains mostly intact NH3 molecules. Strong and Weak Acids In reality the strong acid molecules would be almost completely dissociated in an aqueous solution. The Cl- would remain in solution and free H+ ions would join with available water to form hydronium ions Strong acid H O H H O H H

C O H Cl H C H H dissociated acid molecules O H H

C C O H O H H O H H O H H hydronium molecules

H C H C H O H C O O C O O H H H

O H H H H C O Cl H H H O H

O O O H Cl C H H H C H O H O

H C H H Cl O H H O H H Cl H H

Weak acid H H H H Many intact acid lots of water molecules molecules Few hydronium molecules Conjugate pairs If 2 species differ by just 1 proton they are classed as a conjugate acid-base pair. Examples of acid-base pairs are H2SO4/HSO4- and NH4+/NH3. The acid is always the species with the additional proton. It can also be said that NH3 is the conjugate base of NH4+. 3 Transfer of hydrogen ions in conjugate pairs

When a base accepts a proton, it becomes an acid because it now has a proton that it can donate. And when an acid donates a proton it becomes a base, because it now has room to accept a proton. These are what we call conjugate pairs of acids and bases. When an acid gives up its proton, what remains is called the conjugate base of that acid. When a base accepts a proton, the resulting chemical is called the conjugate acid of that original base. Conjugate Acid and Base pairs (Strong Acid) HX is a symbol used for a strong acid. A conjugate acid can be seen as the chemical substance that releases a proton in the backward chemical reaction. The base produced, X, is called the conjugate base and it absorbs a proton in the backward chemical reaction. paired paired Strong acid HX base

+ transfer of H+ H 2O conjugate base X + conjugate acid H3O+ Conjugate Acid and Base pairs (weak acid) HA is a symbol used for weak acid. Note the use of the double arrow. Because the weak acid only partially dissociates an equilibrium reaction occurs with a fixed amount of an acid and its conjugate remain in solution. paired paired Weak acid

HA base + transfer of H+ H 2O conjugate base A conjugate acid + H3O+ Conjugate Acid and Base pairs (Base) B is a symbol used for a base. The base now accepts the hydrogen ion from the water. The hydroxide ion, OH-, is the paired conjugate of the water once the H+ has been removed. Strong bases use a single direction arrow and weak bases use a double arrow. paired

paired base B + transfer of H+ acid conjugate acid H 2O BH+ conjugate base + OH- Conjugate Acid and Base pairs If 2 species differ by just 1 proton they are classed as a conjugate acid-base pair. Examples of acid-base pairs are H2SO4/HSO4, and NH4+/NH3. The acid is always the

species with the additional proton. It can also be said that NH3 is the conjugate base of NH4+. Base H2O water Conjugate Acid H 3O + SO42 sulfate ion HSO4- NH3 ammonia NH4+ OH- hydroxide ion

H2O HCO3 hydrogen carbonate ion H2CO3 CO32 carbonate ion HCO3- Conjugate Acid and Base pairs The stronger an acid, the weaker its conjugate base, and, conversely, the stronger a base, the weaker its conjugate acid. A strong acid like HCl donates its proton so readily that there is essentially no tendency for the conjugate base Cl to reaccept a proton. Consequently, Cl is a very weak base. A strong base like the H

ion accepts a proton and holds it so firmly that there is no tendency for the conjugate acid H2 to donate a proton. Hence, H2 is a very weak acid. Weak and strong acids pH = -log[H30+] Weak acid less than 5% dissociation HA(aq) + Acid (weak) H20(aq) water A-(aq) conjugate base + H30+(aq) hydronium

Strong acid complete dissociation HX(aq) + H20(aq) X-(aq) + H30+(aq) Where c(HX) = [H30+] Initial concentration of HX is equal to final concentration of H30+ so pH= -log c(HX) Bronsted-Lowry acids and bases summary Proton donation to a water molecule forms H3O+ (hydronium) ions. HA(aq) + H2O(l) H3O+(aq) + A(aq) acid base acid base proton donor proton acceptor

Similarly, proton donation from water to a base produces OH ions. B(aq) + H2O(l) BH+(aq) + OH(aq) base acid acid base proton acceptor proton donor 2015 dissociation equations - NCEA Case Study Achieved Question Question: 1a: (i) Methylammonium chloride, CH3NH3Cl, dissolves in water to form a weakly acidic solution. Ka(CH3NH3+) = 2.29 1011 (a) (i) Write an equation to show CH3NH3Cl dissolving in water. CH3NH3Cl(s) CH3NH3+(aq) + Cl(aq) CH3NH3+ + H2O CH3NH2 + H3O+ 2014 dissociation equations - NCEA Case Study Question: 1a: When chlorine gas is added to water, the equation for the

reaction is: Cl2(g) + H2O(l) HCl(aq) + HOCl(aq) (i) Write an equation for the reaction of the weak acid, hypochlorous acid, HOCl, with water. HOCl + H2O OCl + H3O+ Species in solution A solution is formed by mixing a solute (a dissolved substance) into a solvent (the solution that dissolves the solute. In Aqueous Chemistry the solvent is water, and the solute can be an acid, base or ionic salt. A solute dissolves by bonds being broken between solute particles (endothermic) and new bonds being formed between solute and solvent (exothermic). A small amount of H3O+ and OH- will always be present in water due to Kw = [OH-] [H3O+] = 1 x 10-14 Water will always be present in large concentrations.

Concentration Concentration of species in solution The relative concentration of the species in solution at equilibrium will depend upon the type of substances dissolved into water initially. NaCl in solution 25 In aqueous solutions water will almost always be present in the highest concentration. 20 15 10 Series 3 5 0 Species

Small quantities of H3O+ and OH- will also be present, according to the Kw = [H3O+] [OH-] = 1 x 10-14 Information on relative concentration can often be presented in a bar graph. Weak and strong acids In a strong acid there will be no original acid seen in the final solution. In a weak acid there will be mostly the original acid seen in the final solution. Equal quantities of conjugate base and hydronium are formed Equal quantities of conjugate base and hydronium are formed, but in small amounts

Concentration of ions in solution Strong Acid Strong Acid i.e. HCl reacting with water [Cl-] = [H3O+] > [OH-] Strong acids will provide good conductivity and pH 1-2 due to the high presence of H3O+ ions 0.12 0.1 Concentration HCl mol L-1 0.1 0.1 0.08 Concentration mol L-1 0.06

0.04 0.02 0 10 -13 H3O+ Cl- OH- No strong acid will be left in the final mixture. H3O+ and Cl- are produced in equal concentrations in the same concentration as the original strong acid. A small amount of OHis present as water dissociates into H3O+ and OH- Concentration of ions in solution Weak Acid Weak Acid i.e. CH3COOH reacting with water

[CH3COOH] > [CH3COO-] [H3O+] > [OH- ] weak acids will provide poor conductivity and pH 3-6 due to the low presence of H3O+ ions (but still higher than OH- ions) 0.12 CH3COOH mol L-1 Concentration ~0. 0.1 1 0.08 Concentration mol L-1 0.06 0.04

0.02 0 10-3 CH3COOH CH3COO- 10-3 H3O+ 10-11 OH- Most weak acid will be left in the final mixture. H3O+ and CH3COO- are produced in equal concentrations a small amount of the weak acid had dissociated. A small amount of OH- is present as water dissociates into H3O+ and OH- Concentration of ions in solution Strong Base Strong Base i.e. NaOH reacting with water

[OH-] >= [Na+] > [H3O+] Strong bases will provide good conductivity and pH 12 14 due to the high presence of OH- ions 0.12 0.1 Concentration NaOH mol L-1 0.1 0.1 0.08 Concentration mol L-1 0.06 0.04 0.02 0

10-13 OH- Na+ H3O+ No strong base will be left in the final mixture. OH- and Na+ are produced in equal concentrations in the same concentration as the original strong base. A small amount of H3O+ is present as water dissociates into H3O+ and OH- Concentration of ions in solution Weak Base Weak Base i.e. NH3 [NH3] > [OH-] > [NH4+]

> [H3O+] weak bases will provide poor conductivity and pH 8 11 due to the low presence of OH- ions (but still higher than H3O+ ions) 0.12 0.1 Concentration NH3 mol L-1 ~0. 1 0.08 Concentration mol L-1 0.06 0.04 0.02 0

10-3 10-3 10-11 NH3 NH4+ OH- H3O+ Most weak base will be left in the final mixture. OH- and NH4+ are produced in equal concentrations a small amount of the weak base had dissociated. A small amount of H3O+ is present as water dissociates into H3O+ and OH- Concentration of ions in solution acid salt Acid Salt i.e. NH4Cl [Cl-] > [NH4+ ]

> [H3O+] = [NH3] > [OH-] Acid salts will provide good conductivity and pH < 7 due to the high presence of ions from dissolving and to a lesser extent H3O+ ions NH4Cl mol L-1 Concentration 0.12 0.1 ~0. 0.1 1 0.08 Concentration

mol L-1 0.06 0.04 0.02 0 10-5 10-5 10-9 Cl- NH4+ H3O+ NH3 OH- The spectator ion will be left in the highest concentration followed by the weak acid. H3O+ and NH3 are produced in equal concentrations a small amount of the weak acid had dissociated.

A small amount of OH- is present as water dissociates into H3O+ and OH- Concentration of ions in solution base salt Base Salt i.e. CH3COONa [Na+] [CH3COO-] > [CH3COOH] = [OH- ] > [H3O+] base salts will provide good conductivity and pH > 7 due to the high presence of ions from dissolving and to a lesser extent OH- ions 0.12 0.1 CH3COONamol L-1 Concentration 0.1 ~0. 1 0.08 Concentration

mol L-1 0.06 0.04 0.02 0 10-5 10-5 10-9 Na + CH3COO-CH3COOHOH- H3O+ The spectator ion will be left in the highest concentration followed by the weak base. OH- and CH3COOH are produced in equal concentrations a small amount of the weak base had dissociated. A small amount of H3O+ is present as water dissociates into H3O+ and OH-

pH of salt solutions All cations that are the conjugate acids of weak bases act as weak acids and lower the pH of the solution. This means that a salt solution containing this cation could be acidic. For example, a solution of ammonium chloride, NH 4Cl, contains the cation NH4+ and the anion Cl. The Cl ion acts as a neutral species and does not affect the pH (as it is the conjugate base of a strong acid and is so weakly basic that it effectively has no reaction with water). The NH 4+ ion is the conjugate acid of the weak base NH3 and so itself is a weak acid. The ionic salt will first dissolve into its two ions. This equation needs to be shown. There will then be a further equation as the ion acting as a weak acid or base undergoes a acid/base reaction with water. The non-reacting ion is left off as the spectator. NH4Cl(s) NH4+(aq) + H2O(l) NH4+(aq) + Cl-(aq) NH3(aq) + H3O+(aq) 2015 relative concentration - NCEA Case Study

Question: 1a: (iii) List all the species present in an aqueous solution of CH3NH3Cl, in order of decreasing concentration. Do not include water. CH3NH3+ + H2O CH3NH2 + H3O+ Cl > CH3NH3+ > H3O+ = CH3NH2 > OH OR Cl > CH3NH3+ > H3O+ > CH3NH2 > OH Merit Question 2014 Species present - NCEA Case Study Excellence Question Question: 1a: When chlorine gas is added to water, the equation for the reaction is: Cl2(g) + H2O(l) HCl(aq) + HOCl(aq) (ii) List all the species present when HOCl reacts with water, in order of decreasing concentration. Justify your order. HOCl > H3O+ > OCl > OH or HOCl > H3O+ = OCl > OH

HOCl partially dissociates, and so the equilibrium lies to the LHS/favours the reactants; therefore HOCl is present in the greatest amounts. H3O+ and OCl are produced in equal amounts / there is a small contribution to H3O+ from water therefore H3O+ > OCl Because there is a relatively high [H3O+], the [OH] is very low (or links to Kw). Ba Kn ck ow gro le un dg d e Putting it all together Conductivity of solutions Conductivity is related to the availability of free moving charged particles. The presence of ions in solution and the concentration of them determine conductivity. High conductivity A strong electrolyte (solution containing ions) is created when a strong acid /strong base is added to water and fully dissociates. A ionic salt added to water also produces a strong electrolyte when both anions and cations are formed. Conductive

solution Non-conductive solution Conductivity of solutions Low Conductivity A weak electrolyte is formed from a weak acid or base that only partially dissociates. Only a small concentration of ions are created to carry charge. (such as acetic acid) No Conductivity Polar molecular solids that dissolve in water have no free charge particles (such as glucose or alcohols) and therefore can not conduct charge. ethanoic acid glucose

2015 Conductivity - NCEA Case Study Excellence Question Question: 1b: The table shows the pH and electrical conductivity of three solutions. The concentrations of the solutions are the same. Compare and contrast the pH and electrical conductivity of these three solutions. Include appropriate equations in your answer. The pH of a solution is calculated from its [H3O+]. NaOH is an ionic solid that is a strong base and dissociates completely to produce a high OH concentration (low [H3O+]). Since [OH] is high / [H3O+] is low, the pH is high. NaOH Na+ + OH 2015 Conductivity - NCEA Case Study Question: 1b: The table shows the pH and electrical conductivity of three Excellence Question solutions. The concentrations of the solutions are the same. Compare and contrast the pH and electrical conductivity of these three solutions. Include appropriate equations in your answer. CH3NH2 is a weak base that partially reacts / dissociates / ionises with H2O producing a

lower concentration of OH, Therefore it has a lower pH than NaOH: CH3NH2 + H2O CH3NH3+ + OH The CH3COONa is an ionic solid that dissociates completely in H2O. The CH3COO ion is a weak base that partially reacts / dissociates / ionises with H2O producing a lower concentration of OH. CH3COO + H2O CH3COOH + OH The pH is closer to 7, showing it is the weakest base. Therefore it has a lowest pH 2015 Conductivity - NCEA Case Study Question: 1b: The table shows the pH and electrical conductivity of three Excellence Question solutions. The concentrations of the solutions are the same. Compare and contrast the pH and electrical conductivity of these three solutions. Include appropriate equations in your answer. Electrical conductivity: Electrical conductivity is determined by the concentration of ions. NaOH completely dissolves to produce a high concentration of Na+ and OH ions in solution. NaOH Na+ + OH Therefore it is a good conductor. 2015 Conductivity - NCEA Case Study Question: 1b: The table shows the pH and electrical conductivity of three

Excellence Question solutions. The concentrations of the solutions are the same. Compare and contrast the pH and electrical conductivity of these three solutions. Include appropriate equations in your answer. Electrical conductivity: Since CH3NH2 is a weak base, it only partially reacts with water to produce a low concentration of ions in solution so it is a poor electrical conductor. CH3NH2 + H2O CH3NH3+ + OH CH3COONa is also an ionic solid. It dissolves completely to produce a high concentration of Na+ and CH3COO ions: CH3COONa Na+ + CH3COO Therefore it is a good conductor. Kw the ionic product for water Kw is ionic product for water and an equilibrium constant based on the reaction of water molecules transferring H+ in an acid base reaction to create OH- and H3O+ in equal quantities. The rate of reaction from reactants to products is the same as products to reactants once equilibrium is reached. Kc = [H30+] [OH-] [H20]2 from

2H20(l) H30+(aq) + OH- (aq) (rH =+ve) Or Kc x [H20]2 = [H30+] [OH-] Because the concentration of water is so large it doesnt change considered constant So Kc x [H20]2 is also constant called Kw -14 As [H30+] x [OH ] always equals 1 x 10 thencauses so does Kan w Temperature increase increase in Kw as the reaction is endothermic this favours the forward reaction (Le Chateliers Principle)

Ba Kn ck ow gro le un dg d e Using Kw to Calculate [OH-] or [H3O+] The product [OH-] x [H3O+] is a constant value (at the same temperature) IONIC PRODUCT KW = [OH-] x [H3O+] = 1 x 10-14 e.g. If solution A has [OH-] = 1 x 10-1 molL-1 [H3O+] = 1 x 10 -14 = 1 x 10-13 1 x 10-1 [OH-] = 1 x 10-14 [H3O+] or find [H3O+]

molL-1 [H3O+] = 1 x 10-14 [OH-] Acidity constant An acid dissociation constant, Ka, (also known as acidity constant) is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction known as dissociation in the context of acid-base reactions. The equilibrium can be written symbolically as: The chemical species HA, A and H+ are said to be in equilibrium when their concentrations do not change with the passing of time. Acidity constant Weak acids dissociate only slightly therefore in a solution mostly reactants will be found and the K value will be small Strong acids completely (or nearly completely) dissociate therefore in a solution only a small amount of reactants will be found and the K value will be large Acidity constant

From the equation: HA + H 2O A- + H3O+ The equilibrium constant for a weak acid can be written as: We dont include H2O Ka = [H3O+] [A-] because in an aqueous solution it is [HA] in such high concentrations that the difference before

We can also assume that the concentration of H3O+ and A- are the same, as one mole of and after dissociation H3O+ forms every time one mole of A- is created is negligible. In a weak acid we can assume that the [HA] concentration at equilibrium is no different from the starting concentration c(HA) due to very limited dissociation. Acidity constant - assumptions Acidity constant = Ka [H30+] = [A-] hydronium concentration = conjugate base concentration Ka = [H30+]2 [HA] if Ka small then [H30+] much smaller than [HA] very little dissociation [HA] can then be assumed to be equal to c(HA) [H30+] = Ka x c(HA) pH calculations Weak acid 1. Convert pKa to Ka (if required)

2. Calculate [H3O+] 3. Calculate pH (start here if strong acid) pH calculations Weak acid Ka = [H30+] [A-] [H30+] = Ka [HA] pH = -log[H3O+] [HA] Concentration of water is so large it is not effected considered a constant Use when given Ka (acid dissociation constant) given c(HA) initial concentration of acid, as concentration at equilibrium [HA] and at the start c(HA) is the same weak acid, HA

HA + H20 A- + Use this equation to compare number of mols. H30+ 2015 pH calculations - NCEA Case Study Question: 1a: (iv) Calculate the pH of 0.0152 mol L1 CH3NH3Cl solution. Ka(CH3NH3+) = 2.29 1011 H 3O + = K a HA =5.90 10 7 pH =6.23 [H3O+] = 5.90 107 mol L1 pH = log 5.90 107 = 6.23 Merit Question Pka

larger pKa more reactants pKa = -log Ka negative for strong acids (HX) gets larger (3 13) as acids get weaker less dissociation Weaker acid = stronger conjugate base HA + H 20 reactants H 30 + + A- products Ka = 10-Pka 2014 comparing pH and pKa - NCEA Case Study Merit

Question Question: 1a: Hypochlorous acid has a pKa of 7.53. Another weak acid, hydrofluoric acid, HF, has a pKa of 3.17. A 0.100 mol L1 solution of each acid was prepared by dissolving it in water. Compare the pHs of these two solutions. No calculations are necessary. Hydrofluoric acid is a stronger acid/more acidic/dissociates more because it has a smaller pKa (larger Ka) than hypochlorous acid. So HF will therefore have a higher [H3O+]. As [H3O+] increases, the pH decreases, so HF will have a lower pH than HOCl. (pH HF = 2.09, HOCl = 4.27) larger pKa more reactants, the weaker the acid Bases B(aq) + Base H20

water BH + conjugate acid + OH- hydroxide Strong base completely dissociates (accepts all H+ ions) pH = -log[H30+] [H30+] = 1 x 10-14/[OH-] Strong bases will have a conjugate weak acid Weak base partly dissociates (accepts few H+ ions) [B] assumed to be same as c(B) initial concentration Kb base dissociation constant Kb = 1 x10-14 / Ka [OH-] = Kb x c(B)

Kb is small if Ka is large weak base and strong acid Kb is large if Ka is small strong base and weak acid pH calculations Weak base 2H20(l) [H30+] = K w x Ka [A-] H30+(aq) + OH- Kw = Kc x [H20]2 = [H30+] x [OH-] Because the concentration of water is considered constant [H30+] x [OH-] = 1 x 10-14 Kw = 1 x 10-14 Use when given Ka of conjugate acid (acid dissociation constant) given concentration of reactant weak base, B (replace [A-]) BH+

+ H 20 B + Use this equation to compare number of mols. H 30+ pH calculations Weak base 1. Convert Ka to Kb 2. Calculate [OH-] 3. Convert [OH-] to [H3O+] (start here if Strong Base) 4. Calculate pH Acid base titration curves A plot of the pH of an acid solution against the volume of added base (or

vice-versa) produces what is called a pH titration curve. The example below shows how the pH (measured using a pH meter) changes when a strong acid is added to a strong base. There are characteristic points on the curve that can be identified. One of these is the equivalence point, the midpoint of the section where the pH of the solution rises (or falls) sharply. The equivalence points for titrations between a strong acid and a strong base have a pH of 7. Both before and after this section the pH only changes slowly. Volume of NaOH added / mL Because the pH rises so sharply at the equivalence point of a strong acid/strong base titration a range of indicators can be used to determine the end-point of the titration. If the indicator has a pKa value equal to a pH value

Acid base titration curves The pH curve below shows a typical shape for the titration of a weak acid with a strong base eg methanoic acid with sodium hydroxide. The equivalence point is at a pH greater than 7 so only indicators with a pKa about 8-9 will change at the Note that the equivalence point has a pH > 7 since at this point it is colour a solution of sodium methanoate and the methanoate ion is a weak base sincecorrect it is the pH

and conjugate of the weak acid methanoic acid. At the equivalence point the be useful HCOO formed reacts with water: HCOO- + H2O HCOOH + OH Neutralisation of acids Acids are neutralised by bases. The amount of base needed to neutralise an acid depends only on the concentration and volume and is independent of the acid strength. The concentration of an acid solution is found by carrying out a titration with a base of accurately known concentration (called a standard solution). Such a titration is also called a volumetric analysis. Given the titration data it is possible to calculate the acid concentration. To determine the amount of base needed to neutralise an acid we normally use an appropriate acid-base indicator and stop the titration at the point when the indicator changes

colour. This is called the end-point of the titration. This is the point when the amount of added base is exactly equal to the initial amount of acid in the solution. Neutralisation of acids The pH of the equivalence point will determine the choice of indicator used. Features of a titration curve strong base/weak acid Buffer zone 1 from pKa Mid-point pKa of weak acid Start pH of acid

After equivalence point Equivalence point > pH 7 Features of a titration curve strong base/weak acid 1. Start pH of acid - The initial pH of the solution is due to the starting acid or base in the flask. This is where your titration curve begins 2. Equivalence point - This is the point when all of the weak acid has reacted with the base being added. This will be the most vertical point on the graph. 3. Mid-point This will be exactly half way in volume to the equivalence point. The pka will be the pH of the midpoint. 4. Buffer Zone This will be an area 1 pH either side of the mid - point. It can

be plotted on the graph as a circled area 5. After the equivalence point The pH depends on the concentration of the solution being added from the burette. Acid base titration curves Strong Base added to Strong Acid Characteristics Start point below pH 3 Equivalence point at 7 End of titration below pH12 Symmetrical shape Acid base titration curves Strong Base added to Weak Acid Characteristics Start point above pH 3 Equivalence point above 7

End of titration above pH12 Unsymmetrical shape Acid base titration curves Strong Acid added to Weak Base Characteristics Start point below pH 12 Equivalence point below 7 End of titration below pH3 Unsymmetrical shape Drawing titration curves Step One: Calculate the start pH (in flask) Ka = 10Weak acid [H3O+] = Ka x c(HA) pKa K b = Kw Weak base [OH-] = Kb x c(B)

Assumptions: [HA] = c(HA) H2O concentration is the same before and after [H3O+] = [conj base] Ka Drawing titration curves Step Two: Calculate the volume at equivalence point a) Calculate the number of moles of known acid or base (the substance where the concentration has been given) n=c x b) Multiply the number of moles by U/K v Example if concentration given for NaOH and you are calculating the concentration for H2SO4 H2SO4 2H2O UNKNOWN c) +

2NaOH Na2SO4 + KNOWN Rearrange equation to calculate volume Moles Unknown = Moles known x U/K = Mole Known x 1/2 v = volume (L) c = concentration (MolL-1) v=n/c Drawing titration curves Step Three: Calculate the midpoint Volume of the buffer zone a) Volume ( x axis) = equivalence point volume / 2 b) pH ( y axis) = pKa of the Weak Acid ( or conjugate acid of Weak base) The buffer zone is 1 pH either side of the mid-point Step Four: calculate the pH of equivalence point

n of conjugate base = n of strong base c(conjugate base) = n/v(original + new added) [H3O+] = k a x kw c(conjugate base) Drawing titration curves Step Four: Calculate pH of the equivalence point (end point) a) Use the number of moles (n) of base (as calculated in step two) required to completely react with n of acid present to reach equivalence. Each 1 mole of base required to react with acid produces 1 mole of conjugate base. Example HCOOH(aq) + NaOH(aq) HCOONa(aq) + H2O(l) b) Calculate c( conjugate base) using c = n/v V = initial volume in flask + volume added during titration to reach equivalence c) Use pH equations

Drawing titration curves Step Five: Calculate pH after the equivalence point [OH-] = start concentration x volume added after equivalence total volume acid + base Plot all of these points on the graph and join with a curved line. If the acid or base is weak the curve will be gentle, if the acid or base is strong the curve will be sharp. 2015 Titration Curves - NCEA Case Study Question: 3a: 20.0 mL of 0.258 mol L1 hydrofluoric acid, HF, solution is titrated with a sodium hydroxide, NaOH, solution. The equation for the reaction is: HF + NaOH NaF + H2O pKa(HF) = 3.17 (i) Identify the species in solution at the equivalence point. Na+, F, H2O, HF, OH, H3O+. Achieved

Question 2015 Titration Curves - NCEA Case Study Merit Question Question: 3a: (ii) Explain why the pH at the equivalence point is greater than 7. Include an equation in your answer. A weak base, F, is present at the equivalence point: F + H2O HF + OH This increase in [OH] causes the pH to be greater than 7. Achieved Question 2015 Titration Curves - NCEA Case Study Question: 3a: 20.0 mL of 0.258 mol L1 hydrofluoric acid, HF, solution is titrated with a sodium hydroxide, NaOH, solution. HF + NaOH NaF + H2O

pKa(HF) = 3.17 (iii) After a certain volume of NaOH solution has been added, the concentration of HF in the solution will be twice that of the F. Calculate the pH of this solution, and evaluate its ability to function as a buffer. [H3O+] = 2 x 103.17 = 1.35 x 103 mol L1 pH = log (1.35 x 103) = 2.87. pH = pKa + log [F] / [HF] = 3.17 + log 0.5 = 2.87 Alternative Since there are significant concentrations of the weak acid and method its conjugate base the solution can resist added acid or base. However, since the pH of the buffer solution is less than the pKa, / [HF] > [F], it is more effective against added base than acid. 2015 Titration Curves - NCEA Case Study Excellence Question

Question: 3a: 20.0 mL of 0.258 mol L1 hydrofluoric acid, HF, solution is titrated with a sodium hydroxide, NaOH, solution. HF + NaOH NaF + H2O pKa(HF) = 3.17 (iv) Determine by calculation, the pH of the solution after 24.0 mL of 0.258 mol L1 NaOH solution has been added. . 24 20 =1.032 10 3 mol 1000 n 1.032 10 3 c(NaOH) = = =0.0235 mol L 1 44 v 1000 Kw 110 14 + [H 3O ] = = =4.26 10 13 mol L 1 [OH ] 0.0235

n(NaOH) =cv=0.258 pH = log 4.26 10 13 =12.4 2015 Titration Curves - NCEA Case Study Excellence Question Question: 3b: In a second titration, a 0.258 mol L1 ethanoic acid, CH3COOH, solution was titrated with the NaOH solution. Contrast the expected pH at the equivalence point with the HF titration. pKa(CH3COOH) = 4.76 No calculations are necessary. larger pKa more reactan Since CH3COOH has a higher pKa, it is a weaker acid than HF. Therefore its conjugate base, CH3COO, will be a stronger base than F. This means [OH] will be higher at the equivalence point for the CH3COOH vs NaOH titration, so the equivalence point pH will be higher. 2014 Titration Curve - NCEA Case Study Question: 3a: A titration was carried out by adding hydrobromic acid, HBr,

Excellence Question to 20.0 mL of aqueous methylamine, CH3NH2, solution. The equation for the reaction is: CH3NH2 + HBr CH3NH3+ + Br Ka(CH3NH3+) = 2.29 1011 Explain why the pH does not change significantly between the addition of 5 to 15 mL of HBr (around point A on the curve). At point A, [CH3NH2] [CH3NH3+]. So the solution has buffering properties in the proximity of point A. When HBr is added, the H3O+ is consumed: H3O+ + CH3NH2 CH3NH3+ + H2O Since the H3O+ is removed from the solution (neutralised), the pH does not change significantly. 2014 Titration Curve - NCEA Case Study Question: 3b: A titration was carried out by adding hydrobromic acid, HBr, Excellence Question

to 20.0 mL of aqueous methylamine, CH3NH2, solution. The equation for the reaction is: CH3NH2 + HBr CH3NH3+ + Br Ka(CH3NH3+) = 2.29 1011 The aqueous methylamine, CH3NH2, solution has a pH of 11.8 before any HBr is added. Show by calculation that the concentration of this solution is 0.0912 mol L 1. 2014 Titration Curve - NCEA Case Study Excellence Question Question: 3c: Write the formulae of the four chemical species, apart from water and OH, that are present at the point marked B on the curve. (ii) Compare and contrast the solution at point B with the initial aqueous methylamine solution. In your answer you should include: a comparison of species present AND their relative concentrations a comparison of electrical conductivity linked to the relevant species present in each solution equations to support your answer. . CH3NH3+, Br, CH3NH2, H3O+ 2014 Titration Curve - NCEA Case Study

Question: 3c: (ii) Compare and contrast the solution at point B with the initial Excellence Question aqueous methylamine solution. At the start, before addition of HBr there is a solution of weak base (CH3NH2) which only partially reacts with water to produce a relatively low concentration of ions. As a result, the initial CH3NH2 solution will be a poor electrical conductor. CH3NH2 + H2O CH3NH3+ + OHTherefore species present are CH3NH2 > OH CH3NH3+ > H3O+ At point B, there is a solution of the salt CH3NH3Br present which is dissociated completely into ions. Therefore there is a relatively high concentration of ions (CH3NH3+ and Br) present in the solution, so it will be a good electrical conductor / electrolyte. CH3NH3Br CH3NH3+ + Br CH3NH3+ reacts with water according to the equation CH3NH3+ + H2O CH3NH2 + H3O+ Species present are Br > CH3NH3+ > H3O+ CH3NH2 > (OH) Buffer solutions The pH of aqueous solutions is controlled by the transfer of protons between ions and water molecules. The pH of blood, for example, is normally 7.4, and if it falls more than 0.4 from this value (as a result of disease or shock, both of which generate acidic conditions) then you could die. You could also die if your blood plasma pH rises to 7.8, as could happen during the early stages of recovery from severe burns. To survive, your blood system is buffered to maintain a constant pH. A buffer solution consists of a weak acid (to supply protons to any added strong base)

and its conjugate weak base (to receive protons from any added strong acid). A buffer solution is a solution that resists changes in pH when small amounts of acid or base are added. Buffers make use of equilibrium principles which stabilize the ratio of containing reactants to products An example of a buffer solution would be one a mixture of and change ethanoic acid and sodium ethanoate. If base (OHresist ) ions are added of this Buffer solutions they will react with the ethanoic acid. CH3COOH(aq) + OH(aq)

CH3COO(aq) + H2O(l) If acid (H3O+) ions are added they will react with the ethanoate ions. CH3COO(aq) + H3O+(aq) CH3COOH(aq) + H2O(l) These reactions show that any added acid (H3O+) or base (OH) are largely consumed and the pH of the solution therefore hardly changes. If there is a higher concentration of weak acid then the buffer will work better at neutralising acid and vice versa Buffer calculations for monoprotic acids Calculate pH of buffer given: ka or Pka + conc of [HA] and [A-] Note: in a Rearrange formula

buffer solution HA + H20 H30+ + A[H3O+] does not equal [A-] Ka = [H3O+][A-] to [H3O+] = Ka x [HA] since the A[HA] [A -] has not been produced by the Convert to pH = pKa - log [HA] or pH = pK adissociation + log [A-] of the[HA] acid HA [A-] alone Buffer calculations for monoprotic acids Buffer calculations

[H3O+] = Ka x [weak acid] OR pH = pKa + log [A-] [conjugate base] [HA] [Weak acid or conjugate base] = original concentration x original volume final volume Note: because the buffer solution contains a higher concentration of acid than Buffer capacity The effectiveness of a buffer in maintaining pH depends on the relative concentrations of acid and base in the solution. A buffer solution with a high concentration of acid and base can neutralise more added base and acid than one with low concentrations.

If [weak base] = [weak acid] in a buffer solution, then pH = pKa. Example If a buffer solution is made up of 0.050 mol L-1 benzoic acid and 0.050 mol L-1 sodium benzoate, show that the pH of the solution =4.19, given that pK a(benzoic acid ) =4.19. pH = pKa + log10 = 4.19 + log10 = 4.19 + log10 1.0 = 4.19 Buffer Key Questions definition What happens when an acid or base is added? What is the significance of the half equivalence point?

Buffer solutions Draw a titration curve and show buffer zone What type of acid base titration has a buffer zone? What formula do we use to calculate pH of a buffer solution What pH would a buffer be if we added c(acid) with c(base) and ka given? How could you make this a

better buffer? Excellence Question 2014 buffers - NCEA Case Study Question: 1c: An aqueous solution containing a mixture of HF and sodium fluoride, NaF, can act as a buffer solution. Calculate the mass of NaF that must be added to 150 mL of 0.0500 mol L 1 HF to give a buffer solution with a pH of 4.02. Assume there is no change in volume. M(NaF) = 42.0 g mol1 pKa(HF) = 3.17 [F ][H 3O + ] Ka = [HF] [F ] 10 4.02 10 = 0.0500 [F ] =0.354 mol L 1 3.17 n=cxV 1

n(NaF) =0.354 mol L 0.150 L =0.0531 mol m(NaF) =0.0531 mol 42.0 g mol 1 =2.23 g m= n x M Ba Kn ck ow gro le un dg d e Definitions Acid: A solution that has an excess of H+ ions. Alkali: A base in solution that has an excess of OH- ions. Amphiprotic: A substance that can act as either an acid or a base. Aqueous: A solution that is mainly water. Base: A substance that accepts H+ ions. Neutral: A solution that has a pH of 7. It is neither acidic nor basic. Strong Acid: An acid that has a very low pH (0-4).The H+ ions completely disassociates in solution Strong Base: A base that has a very high pH (10-14). A substance that readily accepts all H+ ions.

Weak Acid: An acid that only partially ionizes in an aqueous solution. That means not every molecule breaks apart. They usually have a pH close to 7 (3-6). Weak Base: A base that only partially ionizes in an aqueous solution. That means not every molecule breaks apart. They usually have a pH close to 7 (8-10). Acid/Base Key concepts Ka and pKa HA + B A+ - BH+ conjugate acid/base titration curves H 2O

+H2O H3O + OH+ species in solution pH calculations buffers conductivity

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